Note: Descriptions are shown in the official language in which they were submitted.
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13ACKGROUND OF THE INV~NTION
This invention rela-tes to fabric sof-tening compositions
for use in laundering operations. More partlcularly, this
invention relates to improved fabric softening compositions
containing a smectite-type clay and a quaternary ammonium com-
pound which provide improved softening effects.
The use of clays in combination with auaternary
ammonium compounds (also referred to herein as "QA" compounds for
convenience) is ex~ensively described in the prior art. U.S.
Patent No. 3,886,075, for example, describes a composition con-
taining a smectite clay, a water-insoluble QA compound and an
"amino compatibilizing agent" which is said to provide fabric
softening and anti-s-tatic effects. U.S. Published Patent
Application No . B305,417 describes a granular laundering compos-
ition comprising a soap based granule, a smectite-type clay and
a quaternary ammonium anti-static agent. In U.S. Patent No .
3,862,058, a clay and a quaternary ammonium compound are added
to a non-soap synthetic detergent compound to provide a granular
laundry detergent composition. U.S. Patent Nos. 3,993,573 and
3,954,632 describe fabric softening compositions containing the
aforementioned clay and QA compounds in combination with a so-
called "acid compatibilizing agent". U.S. Patent No. 4,292,035
discloses a softening composition comprising smectite clay; an
amine or quaternary ammonium compound as a sof-tening agent; and
an anionic surfactant wherein the fabric softening agent is
reacted with the clay to form an "organo-clay complex" prior to
the addition of the anionic surfactant.
A common drawback of the aforementioned softening
compositions oE the prior art is -that they require undu:ly high
concentrations o~ QA compounds -to achieve the desirecl sof-tening
effec-t. Thus, for example, in -the detergent composi-tions des-
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cribed in the examples of ~.S. Patent Nos. 3,862,05~; 3,954,632
and 3,993,573, the weight ratio of clay to QA compound is about
5:1. In U.S. Patent No. 3,948~790 and Published Application
B305,~71, the examples described detergent compositions con-
taining 5%, by weight, of QA compound. The use of such rela-
tively high concentrations of QA compound in the aforementioned
compositions of the piror art has two distinct drawbacks: first,
; since QA compounds are relatively expensive softening agents
compared to clay, it is economically desirable to provide the
desired softening properties using a minimum amount of QA com-
pound relative to the clay in the laundry composition; and
second, the QA compounds being cationic are capable of reacting
with anionic detergents and brighteners present in detergent
compositions, such reactions being preferably avoided insoEar as
; they may inactivate the fabric softener ox adversely affect the
laundering capability of the composition. Consequently, there is
a need in the art for fabric softening compositions containing
minimized amounts of QA compounds but still capable of providing
the desired degree of fabric softening.
Achieving the aforementioned objective is particularly
desirable for laundering compositions intended for use in a soak
plus hand-wash operation as compared to laundry operations in a
washing machine. In the latter operation, clay is inherently
more effective as a soft~ning agent insofar as it comes into
contact with and is deposited upon the surface of the fabric
being laundered during the wash cycle of the machine when the
washing bath is mechanically drained through the fabric.
However, in a hand-wash procedure where the mechanical action is
not sufficient to effect a similar degree of contact between the
fabric and -the clay, significantly larger amounts of clay and
QA compound must be employed to achieve comparable softening of
the fabrics being laundered.
5~
The methods described in the art for preparing the
aforementioned fabric softening compositions are varled. However,
a common characteristic of such processes is their difficulty
in being able to produce a composition capable of providing the
desired degree of fabric softenlng using minimized amounts of
clay and QA compound. The preparation techniques of the prior
art are thus characterized by either a deposition of QA compound
upon granules composed of a uniform blend of clay with detergent
and other ingredients (rather than a preferential deposition
upon clay granules) or alternatively, the QA compound is reacted
with the clay to provide a modified clay in which preferably from
about 10 to about 60 molar percent of the exchangeable cations
are alkyl substituted ammonium ions. Thus, for example, U.S.
Patent Nos. 3,862,058 and 3,~86,075 describe a method of prepar-
ation whereby the clay is initially admixed in a crutcher with
the detergent, builder and other ingredients of the laundering
composition and the resulting mixture then spray-dried to form
granules. The QA compound is thereafter sprayed upon the
granules from a melt, it being a critical aspect of the method
of preparation to avoid spraying the detergent granules with an
aqueous solution or suspension of the QA compound. United States
Published Patent Application B305,417 discloses a ~ethod of
preparation wherein clay is mixed with soap-based granules in a
drum mixer. The QA compound is then added to the resulting
composition by spraying from a melt. U.S. Patent No. 3,594,212
describes a method of softening fibrous materials wherein such
materials are successively impregnated with an aqueous dispersion
of clay and an aqueous solution of QA compound, the amount of QA
compound in solution being sufficient to effect at least a
partial cation exchange with the clay retained on the fibrous
material. In U.S~ Patent No. 3,948,790 to Speakmant there is
described a procedure for preparing "quaternary ammonium clays"
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whereby a QA compound is reacted with clay by slurrying the
untreated clay ln a solution containing the desired quantity of
QA compound. The QA compounds which may be thus employed are
said to be restricted to short-chain compounds having a maximum
of four carbon atoms per chain, the total number of carbon atoms
in the compound not exceeding eight. The quantity of such QA
; compound added to the solution is controlled so as to provide
the desired degree of ion exchange with the clay. The examples
of the patent describe various treated clays in which from about
5 to 40% of the exchangeable cations are replaced by quaternary
ammonium cations, the amount of QA compound in solution being
necessarily restricted to that which is required to effect a
partial exchange reaction with the clay. Accordingly, the prior
art does not contemplate the formation of a surface modiEied
clay as herein described.
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SUMMARY OF THE INVENTION
The present invention provides an improved fabric
softening composition comprising ~i) discrete softening particles
containing at least about 75%, preferably at least 90%, by
weight, of a smectite-type clay, and less than about 5%, by
weight, of detergent surface active agents selected from the
group consisting of anionic, nonionic, ampholytic and zwitter-
ionic detergents; and (ii) a cationic compound selected from the
group consisting of primary, secondary and tertiary amines and
their water-soluble salts, diamine and diammonium salts, and
quaternary ammonium~ phosphonium and sulfonium compounds,
substantially all of said cationic compound being adsorbed upon
the surface of said softening particles.
The term "softening particles" as used throughout the
specification and claims is intended to encompass a wide variety
of particulate matter of differing shape, chemical composition,
particle size and physical character-stics, the essential common
characteristic being that such softening particles contain at
least 75%, and preferably at least 90%, by weight, of a
smectite-type clay, the primary softening ingredient in the
softening compositions of the invention. The weight percent of
the "smectite-type clay" refers to the weight of the smectite
; clay minerals (e.g., montmorillonite) as well as the water and
impurities associated with the particular clay employed.
Accordingly, the softening particles may be in the form of
finely divided powders, as well as relatively larger-sized
granules, beads or agglomerated particles, and may he produced
by diverse methods of manufacture such as spray-drying, dry-
blending or agglomeration of individual components. Particularly
preferred softening particles for use herein are bentonite
3r~
agglomerates produced by the method described in United States
Patent No. 4,488,972, issued December 18, 1984. The softening
particles may thus optionally include in addition to the
smectite-type clay, materials which do not in-terfere with the
desired fabric softening or with laundering, in general, examples
of suitable ma-terials including binding or agglomerating agents,
e.g., sodium silicate, dispersing agents, detergent builder
salts, filler salts as well as common minor i.ngredients present
in conventional
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laundry detergent compositions such as dyes, optical brighten-
ers, anti-redeposition agents and the like. For purposes of
the invention, the softening particles should contain less than
5%, by weight, of surface active detergent compounds other than
a cationic detergent, preferably less than about 3%, by weight,
and most preferably are substantially free of anionic, nonionic,
ampholytic and zwitterionic detergents.
The term "discrete" as used herein with regard to the
softening particles refers to the fact that such particles are
employed in the present invention as individually distinct
particles, thus excluding, for example, softening particles which
are encompassed within a matrix of other materials, or which are
blended with other ingredients such that the particles become a
component of a larger aggregate material rather than being in
the form of individual and distinct particles.
The cationic compounds suitable for the invention
encompass the aforementioned compounds all of which are capable
of providing a cationic surface to particles of a smectite-type
clay when such compounds are adsorbed upon the surface of the
clay particles as herein described. Quaternary ammonium
compounds are especially preferred for this purpose.
In accordance with the process of the invention, the
above-de~ined fabric softening composition is prepared by a
process comprising the steps of (a) providing softening parti-
cles containing at least about 75%, by weight, of a smectite-
type clay and less than about 5%, by weight, of surface active
detergent compounds other than cationic detergents; and (b)
contacting said particles with a cationic compound such that
substantially all of said cationic compound is adsorbed upon the
surface of said particles and forms at least a partial coating
thereupon.
The step of contacting the softening particles in the
--6--
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above described process of preparation is directed to methods
of depositing a cationic compound upon the surface of the clay-
containing particles rather than methods of effecting a reaction
between such cationic compound and the clay. Thus, the process
of the invention is concerned with avoiding the transformation
of a major portion of the clay to a complex by an ion exchange
reaction, thereby excluding, for example, the methods of pre-
paring a 'IQA clay" and an "organo-clay complex" referred to in
U.S. Patent Nos. 3,94~,790 and 4,292,035, respectively. To
promote the adsorption of a cationic compound upon the surface
of the softening particles, process conditions which favor
swelling of the smectite-type clay are generally avoided so as
to minimize the likelihood of an undesired exchange reaction be-
tween the clay and the cationic compound. Swelling of the clay
ia particularly favored in an aqueous slurry, hence, the less
water which contacts the clay, the less the likelihood of
effecting a cation exchange reaction. Accordingly, the weight
of a~ueous solution which contacts the softening particles in
the method of preparation of the invention is generally restric-
ted to an amount less than the weight of the softening particles,preferably below 50% and more preferably below 25%, by weight,
of such particles.
A preferred method of preparation comprises spraying
the surface of the softening particles with a substantially non-
aqueous solution or suspension containing the cationic compound,
the concentration of water in such solution or suspension being
maintained generally below about 50%, by weight, and preferably
below about 10~, by weight. This is conveniently effected by
spraying the solution or suspension of cationic compound from a
pressurized nozzle so as to produce droplets or a fine mist which
contact the surface of the particles, the latter being conven-
:iently on a moving belt, such as a conveyor belt. The range of
-7
~22~3~6
suitable droplet size may vary widely from about 10 to about 250
microns in diameter, but preferably should be as small as pos~
sible rela-tive to the diameter of the par-ticles being sprayed.
Spraying is preferably carried out at ambient temperatures and
generaly below 100F. At temperatures above 100F, particularly
above 140F, the cationic compounds may be undesirably absorbed
into the softening particles rather than remain as a coating upon
the particl~ surface where it is believed to provide the optimum
softening effect. Any organic solvent in which the cationic
compound can be dispersed may be conveniently employed to form
a solution or suspension for contacting the softening particles.
Useful solvents include propylene glycol, hexylene glycol,
ethanol and isopropyl alcohol.
The present invention is characterized by effective
softening compositions which contain minimized concentrations
of QA compound relative to clay. The invention is predicated
upon a method of preparation wherein substantially all of the
cationic compound used for softening is contacted with the
softening particles as herein described rather than, as disclosed
in the prior art, upon granules of a detergent composition where-
in the clay is only a relatively minor component, usually less
than about 12% of the detergent ~ranule. Thus, the method of
the invention provides for a preferential deposition of QA
compound upon clay. Moreover, unlike the methods of preparation
described in the art wherein a slurry of clay is formed in a
solution of QA compound to effect an ion exchange reaction
therebetween, the present invention provides a surface-modified
softening particle by a method o:E preparation which minimizes
the likelihood of ion exchange between the clay and the cationic
compound, and instead, promotes the formation of at least a
partial surface coating of cationic compound upon the clay
particles by adsorption. This has the effect of maximizing the
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~222356
softening properties which can be provided by the given amount
of clay and cationic compound employed. The surface modified
particles are generally hydrophobic in nature, the clay itself
being hydrophilic. The hydrophobicity of the particles is
particularly advantageous in hand-wash laundering operations
because the hydrophobic particles are not as readily dispersible
in the a~ueous hand-wash solution as untreated clay and, there-
fore, tend to remain upon the surface of the wash solution for
longer periods of time. This has the effect of enhancing the
availability of such particles for contact with and deposition
upon the fabrics being laundered. Thus, the present compositions
are capable of providing improved softening eEfects, particularly
for soak plus hand-wash operations, but at reduced concentrations
of cationic compounds in the softening composition.
Although the applicant does not which to be bound to
any particular theory of operation, it is believed that the im-
proved fabric softening achieved with the compositions of the
present invention is primarily attributable to the surface
modification of the clay-containing particles. Specifically,
the deposition of a cationic compound upon the particle surface
provides a positive charge to such particle thereby creating a
driving force for the positively charged particles of clay to
attach themselves to the negatively charged surface of the
fabrics being laundered, and particularly to fabrics containing
substantial amounts of cotton. The amount of cationic compound
required to impart such surface charge is relatively minor, the
surface modified particles providing no significant antistatic
effect such as said to be provided by the aforementioned compos-
itions of clay and QA compounds known in the art. Thus, it is
3~ believed that the cationic compounds in the compositions of the
invention serve primarily to impart a positive surface charge
to the particles of clay, and consequently, only rela-tively minor
amounts of cationic compounds are required for the present
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compositions compared to softening compositions known in the art.
The fabric softening compositions of the invention con-
tain two essential ingredients: so~tening particles and a cat-
ionic compound. The weight ratio of the softening particles to
cationic compound in the composition is generally from about
500:1 to about 10:1, and preferably from about 200:1 to about.
25:1. Such compositions may be conveniently employed during
home laundering as additives to a laundry detergent compositi.on.
Alternatively, the present invention contemplates incorporating
the above-defined softening compositions into a conventional
laundry detergent composition to form a fully-formulated laundry
detergent composition which contai.ns as a component thereof a
softening composition as defined hereinabove in combination with
an organic detergent compound, a detergent builder salt and other
components optionally present in conventional laundry composi-
tions. The addition of such a fully formulated laundering com-
position to water produces a laundering bath capable of provid-
ing the deisred degree of cleaning and softening of soiled and/or
stained fabrics.
DETAILED DESCRIPTION OF THE INVENTION
The fabric softening compositions of the invention are
suitable as additives to or components of a granular laundry
detergent composition or alternatively improved softening may
be effected by adding the softening compositions to the wash
solution separately from the detergent composition, such as,
for example, during the rinse cycle of a washing machine. The
softening compositions comprise (a) ~iscret.e softening particles
containing at least 75%, by weight~ of a smectite--type clay and
(b) a cationic compound, the ratio of (a) to (b) being generally
from about 500:1 to about 10:1, preferably from about 200:1 to
about 25:1, and most preferably from about 100:1 to about 40:1.
~, i -10-
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The fully formulated laundry detergent composition o~
the invention contains as a component thereof a fabric soften-
ing composition as defined hereinabove in combination with an
organic detergent compound, a detergent builder salt and other
components such as binders/ fillers, brighteners, perfumes,
dyes, foam stabilizers, anti-redeposition agents and the like
which are optionally present in laundry compositions.
Accordingly, such laundry detergent compositions generally
comprise (a) from about 3 to about 50%, by weight, of a fabric
softening composition comprising (i) discrete softening parti-
cles containing at least about 75%, by weight, of a smectite-type
clay, and less than about 5%, by weight, of surface active
detergent compounds other than cationic detergents; and (ii) a
cationic compound selected from the group consisting of primary,
secondary and tertiar~ amines and their water-soluble salts,
diamine and diammonium salts, and quaternary ammonium, phosphon-
: ium and sulfonium compounds, substantially all of said cationic
compound being adsorbed upon the surface of said particles and
forming at least a partial coating thereupon; (b) from about 2
to about 50%, by weight, preferably from about 5 to about 30%,
by weight, of a surface active detergent compound selected from
the group consisting of anionic, nonionic, cationic, ampholytic
and zwitterionic detergents; and (c) from about 1 to about 70%,
by weight, of a detergent builder salt.
The smectite-type clays of the invention are three-
layer clays characterized by the ability of the layered structure
to increase its volume several-fold by swelling or expanding when
in the presence of water to form a thixotropic gelatinous
substance. There are two distinct classes of smectite-type
clays: in the first class, aluminum oxide is present in the
silicate crystal lattice; .in the second class, magnesium oxide
is present in the silicate crystal lattice. Atom subst:itution
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by iron, magnesium, sodium, potassium, calciu~ and the like can
occur within the crystal lattice of the smectite clays. It is
customary to distinguish between clays on the basis of their
predominant cation. For example, a sodium clay i5 one in which
the cation is predominantly sodium. For purposes of the present
invention, aluminum silicates wherein sodium is the predominant
cation are preferred, such as, for example, bentonite clays.
Among the bentonite clays, those from Wyoming (generally referred
to as western or Wyoming bentonite) are especially preferred.
Preferred swelling bentonites are sold under the
trademark Mineral Colloid, as industrial bentonites, by Benton
Clay Company, an affiliate of Georgia Kaolin Co. These materials
which are the same as those formerly sold under the trademark
THIXO-JEL, are selectively mined and beneficiated bentonites,
and those considered to be most useful are available as Mineral
Colloid No's. 101, etc, corresponding to THIXO-JELs No's. 1, 2~ 3
and 4. Such materials have pH's (6% concentration in water) in
the range of 8 to 9.4, maximum free moisture contents of about
8% an~ specific gravities of about 2.6, and for the pulverized
grade at least about 85% (and preferably 100%) passes through
a 200 mesh U.S. Sieve Series sieve. More preferable, the benton-
ite is one wherein essentially all the particles (i.e., a-t least
90% thereof, preferably over 95%) pass through a No. 325 sieve
and most preferably all the particles pass through such a sieve.
The swelling capacity of the bentonites in water is usually in
the range of 3 to 15 ml/gram, and its viscosity, at a 6% con-
centration in water, is usually from about 8 to 30 centipoises.
In a particular preferred embodiment of the invention,
the softening particles comprise agglomerates of finely divided
bentonite, of particle sizes
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less than No. 200 sieve, agglomerated to particles of sizes essentially in
the No's. 10-100 sieve range, of a bulk density in the range of 0.7 to O.g
g./ml. and a moisture content of 8 to 13%. Such agglomerates include about
1 to 5% of a binder or agglomerating agent to assist in main~aining the
integrLty of the agglomerates until they are added to water, in which it is
intended that they disintegrate and disperse. A detailed description of the
method of preparation of such agglomerates is set forth in the aforemen-
tioned U.S. Patent No. 4,488,972 issued December 1~9 1984.
Instead of utilizing the THIXO-J~L* or Mineral Colloid bentonites
one may employ products, such as that sold by American Colloid Company,
Industrial Dlvision, as General Purpose Bentonite Powder, 325 mesh, which
has a minimum of 95% thereof finer than 325 mesh or (~l~ microns in diameter
(wet particle size) and a minimum of 96% finer than 200 mesh or 74 microns
diameter (dry particle size). Such a hydrous aluminum silicate is comprLsed
principally of montmorillonite (90% minimum~, with smaller proportions of
feldspar, biotite and selenite. A typical analysis, on an "anhydrous"
basis, is 63.0% silica, 21.5% alumina, 3.3% of ferric iron (as Fe203), 0.4%
of ferrous iron (as FeO), 2.7% of magnesium (as MgO), 2.6% of sodium and
potassium (as Na20). 0.7% of calclum (as CaO), 5.6% of crystal water (as
H20~ and 0.7% of trace elements.
Although the western bentonites are preferred it is also possible
to utilize other bentonites, such as those which may be made by treating
Italian or similar bentonites containing relatively small proportions of
exchangeable monovalent metals (sodium and potassium) with alkaline materi-
als, such as sodium carbonate, to increase the cation exchange capacities of
such products. It is considered that the Na20 content of the bentonite
should be at least about 0.5%, preferably at least 1% and more preferabiy at
least 2~ so that the clay will be satisfactorily swelling, with good soften-
ing and dispersing properties in aqueous suspension. Preferred swelling
bentonites of the types described above are sold under the trade names
Laviosa* and
* Trade Mark
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"~iJ
3~i~
Winkelmann*, e.g., Laviosa AGs and Winkelmann C 13.
The silicate, which may be employed as a binder to
hold together the finely divided bentonite particles in agglo-
merated form, is preferably a sodium silicate of Na2O:SiO2 e.g.,
1:2.4. The silicate is water soluble and solutions thereof
at concentrations up to about 50%, by weight, may be employed
in the preparation of the aforementioned bentonite agglomerates,
all of such solutions being free flowing, especially at the
elevated temperatures to which the silicate solution is prefer-
ably heated during the preparation procedure.
The cationic compounds are employed in the fabricsoftening compositions of the invention in an amount of from
about 0.2 to about 16%, and preferably from about 1 to 5%, by
weight. In the detergent compositions of the invention, the
cationic compounds are present in an amount of from about 0.01
to about 10%, more usually from about 0.05 to 2%, and preferably
from about 0.1 to 1%, by weight. A uni~ue characteristic of this
invention is the ability to provide effective fabric softening
with detergent compositions wherein the concentration of cationic
compound is as low as 0.05%, by weight, and occasionally lower.
The improved softening effects achieved with the compositions
of the invention are most pronounced in laundry washing baths
containing relatively low concentrations of laundry detergent
compositions, i.e., concentrations of from about 0.1 to 0.7%, by
weight. In general, a concentration of cationic compound in the
laundry washing bath of from about 10 to about 200 ppm is useful
for most laundering operations.
The useful primary, secondary and tertiary amines and
their water~soluble salts are generally of the formula
RlR2R N, wherein Rl represents an alkyl or alkenyl group contain-
ing from about 8 to 22 carbon atoms and R2 and R3 each represent
hydrogen or hydrocarbyl groups containing from 1 to 22 carbon
atoms, the term "hydrocarbyl group" encompassing alkyl, alkenyl,
*Trade mark -13-
aryl and alkaryl groups including substituted groups of this
type, common substituents being hydroxy and alkoxy yroups.
Within the general description of amines yiven above,
specific examples
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include primary tallow amine, primary coconut amine~ secondary tallow methyl
amine, tallow dimethyl amine, tritallow amine, primary tallow amine hydro
chloride, and primary coconut amine hydrochloride.
The useful diamine and diammonium salts have the general formulas:
RlR~NR5NR3R4; [RlR2NR5NR3R4R6]+~ ; [RlR2R3NR5NR4R6~X_;
[RlR2R3NR5NR4R6R7]~X-; wherein Rl, R2, and R3 are as defined above, R4, R6
and R7 have the same definition as R2 and R39 and R5 is an alkylene chain
having from 4 to 6 carbon atoms wherein the middle carbon atoms may be
linked to each other by an ether oxygen or by a double or triple bond. X~
is an anion, preferably chloride, bromide, sulEate, methyl sulfate or simi-
lar anion.
Specific examples of diamines and diamine salts include N-coco-
1,3-diaminopropane, N-tallow-1,3-diaminopropane, n-oleyl-1,3-diaminopropane,
N-tallow-1,3-diaminopropane dioleate and N-tallow-1,3-diaminopropane diace
tate.
Also suitable for use herein are the ethoxylated amine and diamine
salts with fatty alkyl groups of coconut, tallow and stearyl and containing
from about 2 to 50 moles of ethylene oxide. The useful quaternary ammonium
compounds are generally of the formula [RlR2R3R4N]~X-, wherein Rl, R2, R3
and X are as defined above, R4 is an organic radical selected from among
those deEined for Rl, R2 and R3. Although not indicated in the above
formula, Rl and/or R4 may be attached to the quaternary nitrogen atom
through an ether, alkoxy, ester or amide linkage. Among the quaternary
ammonium compounds known to add substantivity to fabrics, particularly
fabrics containing substantial amounts of cotton, three basic types are
particularly useful for the invention: (1) alkyl dimethyl ammonium
compounds; (2) amido alkoxylated ammonium compounds; and (3) alkyl amido
imidazolinium compounds. A detailed description of these three types of
compounds is set forth by R. Egan in Journal American ~ . ~. ~ ,
January, 1978 (vol. 55), pages 118-121.
3~
Long chain quaternary ammonium compounds are generally
preferred for use herein, namely, compounds wherein the number
of carbon atoms is greater than eight. Within the more general
description provided above concerning quaternary ammonium com-
pounds useful for the invention, preferred specific quaternary
ammonium compounds include di-hydrogenated tallow dimethyl
ammonium methyl sulfate; di-hydrogenated tallow dimethyl ammonium
chloride, and l-methyl-l-alkylamidoethyl-2-alkylimidazolinium
methyl sulfate wherein the "al~yls" are oleyl or saturated
hydrocarbyls derived from tallow or hydrogenated tallow.
Dimethyl alkyl benzyl quaternaries that are useful include those
wherein the alkyl group is of a mixture of alkyls of 10 to 18
carbon atoms or 12 to 16 carbon atoms, e.g., lauryl, myristal
and palmityl. The various materials mentioned above are avail-
able commercially from various manufacturers, those from Sherex
Chemical Company being identified by trade marks such as Adogen;
Arosurf: Variquat; and Varisoft.
The quaternary ammonium salts employed herein are
preferably substantially free of a conductive salt; the term
"conductive salt" being used herein to refer to salts which are
electrically conductive in aqueous solution. The conductive
; salts generally have a cation anion-bond of at least 50% ionic
character as calculated in accordance with the method described
in Pauling, I'The Nature of the Chemical Bond", 3rd Edition,
1960. By use of the term "substantially free" is meant a con-
centration of conductive salt less than that present at normal
impurity levels in the quaternary ammonium compound. Generally,
the concentration of conductive salt is below 1%, by weight.
In accordance with another embodiment of the invention,
finely divided softening particles as described above are bonded
to the surface oE a granular detergent composition which is
devoid of a soap to form agglomerate particles consistlng of
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detergent-base granules encapsulated within a surface coa-ting of
smectite clay. The agglomerate particles are characterized by
an inner portion consisting of the detergent-base granules, and
a surface portion contacting and surrounding such inner portion
consisting essentially of softening particles containing at least
about 75~, by weight, and preferably greater than about 90%, by
weight of a smec-tite-type clay and less than about 5~, by weight,
of surface active detergent compounds, preferably substantially
free of such surfactants. A cationic compound as defined above
is adsorbed upon the surface portion of the agglomerate particles.
To achieve a substantially continuous external
surface of clay on the agglomerate particle, the softening
particles employed are as small as possible relative to the
detergent-base granules, allowing the softening particles to be
closely packed around the granules. The detergent composition
granules are preferably spray-dried particles having sizes
within mesh No. 8 to 100, U.S. Sieve Series. The softening
particles are preferably sufficiently small that they pass through
a No. 325 mesh screen, U.S. Sieve Series. The weight ratio
of detergent composition granules to the clay-containing parti-
cles may vary from about 10:1 to about 1:2, preferably from about
5:1 to 1:1. The application of the softening particles to the
base detergent granules may be effected by standard agglomeration
techniques and equipment. One method that has been found to ~e
especially useful is to mix the desired weights of the detergent
composition granules and finely divided clay powder and while
mixing, spray water on to the moving surfaces thereof, or more
preferably, spray a dilute sodium silicate solution. Spraying
may be carried out at room temperature and should be gradual
enough so as to prevent any ob~ectionable lumping of the mi~ture.
Mixing will continue in this manner until the clay particles
a:Ll adhere to the detergent-base yranules, after which m:ixing
-16-
. !~
i~
23~6;
may be halted and the product may be screened or otherwise clas-
si~ied to be wlthin the desired product size range. The silicate
solution employed is normally at a concentration of about 0.05
to 10%, by weight, typically from about 1 to 6%, by weight.
The amount of silicate solution applied to the detergent-base
granules generally constitutes from about 0.01 to about 2%, by
weight. Satisfactory agglomeration and surface coating are
obtained at such concentration using suitable agglomerating
equipment, such as an o~srien agglomerator, or a conventional
inclined drum equipped with spray nozzles, baffles, etc. The
silicate concentration should not be so high as to inhibit dis-
persion of the softening particles in the wash solution when
the product is employed in laundry operations. Although it is
preferred that silicate be employed in the agglomerating spray,
useful product is obtainable by utilizing water alone as an
agglomerating or binding agent or by employing aqueous solutions
of other binders, such as gums, resins and surface active agents.
The adsorption of the cationic compound upon the
surface of the agglomerate particle is carried out using the same
methods described herein with regard to providing a cationic
surface to the so~tening particles. The resulting agglomerate
particles are useful laundry products in which the detergent-base
granule dissolves and functions in the standard manner in the wash
solution while the softening particles become dispersed in the
wash solution where they ser~e as fabric softeners in accordance
with the invention.
As noted above, the softening compositions of the
invention are prepared by a method in which substantially all of
the cationic compound in the softening composition is adsorbed
on the surface oE the softening particles. The process is
preferably effected by spraying a non-aqueous solution of a
cationic compound from a pressuri~ed noz~le over the clay
-17-
~2Z2~5~
particles containing in a rotating drum, or a tube inclined at a
slight angle, such as, from about 5 to 15, the rotational speed
being suitably from about 5 to 100 rpm. Alternatively, spraying
may be effected while the particles are transported on a moving
belt such as a conveyor belt. In accoxdance with another embodi-
ment of the process of preparation, the particles are placed on
a vibrating conveyor belt which is continuously wetted with
a solution or suspension of the cationic compound, the effect
of the vibration being to impart at least a partial coating of
the cationic solution or suspension upon the surface of the
particles.
The laundry detergent compositions with which the
present fabric softening compositions may be incorporated or
with which it may be employed may contain one or more surface
active agents selected from the group consisting of anionic,
nonionic, cationic, ampholytic and zwitterionic detergents. The
synthetic
:
~17a-
~Z~ ;i6
organic detergents employed in the practice of the invention may
be any of a wide variety of such compounds which are well known
and are described at length in the text "Surface Active Agents
and Detergents", ~ol. II, by Schwartz, Perry and Berch,
published in 1958 by Interscience Publishers.
The detergent compositions of the invention preferably
employ one or more anionic detergent compounds as the primary
surfactants. The anionic detergent may be supplemented, if
desired, with another type of surfactant, preferably an
ampholytic detergent. The use of a nonionic detergent is
generally less preferred for the present invention, however,
when used in combination with a detergent builder salt, nonionic
detergents can be advantageously utilized in the present
compositions.
Among the anionic surface active agents useful in the
present invention are those surface active compounds which
contain an organic hydrophobic group containing from about 8 to
26 carbon atoms and preferably from about lQ to 18 carbon atoms
in their molecular structure and at least one water-solubilizing
group selected from the group of sulfonate, sulfate, carboxylate,
phosphonate and phosphate so as to form a water-soluble
detergent.
Examples of suitably anionic detergents include soaps,
such as, the water-soluble salts (e.g., the sodium, potassium,
ammonium and alkanol-ammonium salts) of higher fatty acids or
resin salts containing from about 8 to 20 carbon atoms and
preferably 10 to 18 carbon atoms. Suitable fatty acids can bè
obtained from oils and waxes of animal or vegetable origin, for
example, tallow, grease, coconut oil and mixtures thereof.
Particularly useful are the sodium and potassium salts of the
-18-
J~
, . ,~, .
~2Z~ i6
fatty acid mixtures derived from coconut oil and ~allow, for
example, sodium coconut soap and potassium tallow soap.
The anionic class of detergents also includes the
water-soluble sulfated and sulfonated detergents having an
aliphatic, preferably an alkyl radical containing from about 8
to 26, and preferably from about 12 to 22 carbon atoms. (The
term "alkyl" includes the alkyl portion of the higher acyl
radicals). Examples of the sulfonated anionic detergents are
the higher alkyl mononuclear aromatic sulfonates such as the
higher al~yl benzene sulfonates containing from about lO to 16
carbon atoms in the higher alkyl group in a straight or branched
chain, such as, for example, the sodium, potassium and ammonium
salts of
18a-
~Z23~
higher alkyl benzene sulfonates, higher alkyl toluene sulfonates
and higher alkyl phenol sulfonates~
Other suitahle anionic detergents are the olefin
sulfonates including long chain alkene sulfonates, long chain
hydroxyalkane sulfonates or mixtures of alkene sulfonates and
hydroxyalkane sulfonates. The olefin sul~onate detergents may
be prepared in a conventional manner by the reaction of SO3 with
long chain olefins containing from about 8 to 25, and preferably
from about 12 to 21 carbon atoms, such olefins having the formula
RCH=CHRl wherein R is a higher alkyl group of from about 6 to 23
carbons and Rl is an alkyl group containing from about 1 to 17
carbon atoms, or hydrogen to ~orm a mixture of sultones and
alkene sulfonic acids which is then treated to convert the sul-
tones to sulfonates. Other examples of sulfate or sulfonate
detergents are paraffin sulfonates containing from about 10 to
: 20 carbon atoms, and preferably from about 15 to 20 carbon atoms.
The primary paraffin sulfonates are made by reacting long chain
alpha olefins and bisulfites. Paraffin sulfonates having the
sulfonate group distributed along the pàraffin chain are shown
in U.S. Nos. 2,503,280; 2,507,038; 3,260,741; 3,372,188 and
German Patent No. 735,096.
Other suitable anionic detergents are sulfated
ethoxylated higher fatty alcohols of the formula R~(C2H4O)mSO3M,
wherein R is a fatty alkyl of from 10 to 18 carbon atoms, m is
from 2 to 6 (preferably having a value from about 1/5 to 1/2 the
number of carbon atoms in R) and M is a solubilizing salt-form-
ing cation, such as an alkali metal, ammonium, lower alkylamino
or lower alkanolamino, or a higher alkyl benzene sulfonate
wherein the higher alkyl is of 10 to 15 carbon atoms. The
proportion of ethylene oxide in the polyethoxylated higher alkan-
ol sulfate is preferably 2 to 5 moles of ethylene oxide groups
per mole of anionic detergent, with three moles being most
--19--
:''.
~2æ3~
preferred, especially when the higher alkanol is of 11 to 15
carbon atoms. To maintain the desired hydrophile-lipophile
balance, when the carbon atom content of the alkyl chain is in
the lower portion of the lO to 18 carbon atom range, the ethyl-
ene oxide content of the detergent may be reduced to about two
moles per mole whereas when the higher alkanol is of 16 to 18
carbon atoms in the higher part of the range, the number of
ethylene oxide groups may be increased to ~ or 5 and in some
cases to as high as 8 or 9. Similarly, the salt-forming cation
may be altered to obtain the best so]ubility. It may be any
suitably solutilizing metal or radical but will most frequently
be alkali metal, e.g., sodium, or ammonium. If lower alkylamine
or alkanolamine groups are utilized the alkyls and alkanols will
usually contain from 1 to 4 carbon atoms and the amines and
alkanolamines may be mono- di- and tri-substituted, as in mono-
ethanolamine, diisopropanolamine and trimethylamine. A preferred
polyethoxylated alcohol sulfate detergent is available from
Shèll Chemical Company and is marketed as Neodol 25 3S. (Trade
mark)
The most highly preferred water-soluble anionic
detergent compounds are the ammonium and substituted ammonium
(such as mono, di and tri-ethanolamine), alkali metal (such as,
sodium and potassium) and alkaline earth metal ~such as, calcium
and magnesium) salts of the higher alkyl benzene sulfonates,
olefin sulfonates and higher alkyl sulfates. Among the above-
listed anionics, the most preferred are the sodium linear alkyl
benzene sulfonates (LABS), and especially those wherein the alkyl
group is a straight chain alkyl radical of 12 or 13 carbon atoms.
The nonionic synthetic organic detergents are
characterized by the presence of an organic hydrophobic group
and an organic hydrophilic group and are typically produced by
the condensation of an organic aliphatic or alkyl aromatic hydro-
-20-
3~i~
phobic compound with ethylene oxide (hydrophilic in nature).
Practically any hydrophobic compound having a carboxy, hydroxy,
amido or amino group with a free hydrogen attached to the
nitrogen can be condensed with ethylene oxide or with the poly-
hydration product thereof, polyethylene g]ycol, to form a nonionic
detergent. The length of the hydrophilic or polyoxyethylene
chain can be readily adjusted to achieve the desired balance
between the hydrophobic and hydrophilic groups.
The nonionic detergent employed is preferably a
poly-lower alkoxylated higher alkanol wherein the alkanol is of
10 to 18 carbon atoms and wherein the number of moles of lower
alkylene oxide tof 2 or 3 carbon atoms) is from 3 to 12. Of such
materials it is preferred to employ those wherein the higher
alkanol is a higher ~atty alcohol of 11 to 15 carbon atoms and
which contain from 5 to 9 lower alkoxy groups per mole. Prefer-
ably, the lower alkoxy is ethoxy but in some instances it may
be desirably mixed with propoxy, the latter, if present, usually
being a minor (less that 50~) constituent. Exemplary of such
compounds are those wherein the alkanol is of 12 to 15 carbon
atoms and which contain about 7 ethylene oxide groups per mole,
e.g., Neodol ~ 25-7 and Neodol 23-6.5, which products are
made by Shell Chemical Company, Inc. The former is a condensa-
tion product of a mixture of higher fatty alcohols averaging
about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide
and the latter is a corresponding mixture wherein the carbon atom
content of the higher fatty alcohol is 12 to 13 and the number
of ethylene oxide groups per mole averages about 6.5. The
higher alcohols are primary alkanols. Other examples of such
detergents include Tergitol ~ 15-S-7 and Tergitol 15-S-9, both
of which are linear secondary alcohol ethoxylates made by Union
Carbide Corpor~tion. The former is a mixed ethoxylation product
of an 11 to 15 carbon atom linear secondary alkanol with seven
21-
~:2~3~
moles of ethylene oxide and the latter is a similar product
but with nine moles of ethylene oxide being reacted. Also
useful in the present compositions are the higher molecular
weight nonionics, such as Neodol 45-ll, which are similar ethyl-
ene oxide condensation products of higher fatty alcohols, the
higher fatty alcohol being of 14 to 15 carbon atoms and the
number of ethylene oxide groups per mole being about ll. Such
products are also made by Shell Chemical Company.
Zwitterionic detergents such as the betaines and
sulfobetaines having the following formula are also useful:
2 \
R / ~ -R4 ~ = o
R3
wherein R is an alkyl group containing from about 8 to 18 carbon
atoms, R2 and R3 are each an alkyl or hydroxyalkyl group con-
taining about l to 4 carbon atoms, R4 is an alkylene or hydroxy-
alkylene group containing l to ~ carbon atoms, and X is C or
S:O. The alkyl group can contain one or more intermediate
linkages such as amido, ether, or polyether linkages or non-
functional substituents such as hydroxyl or halogen which do not
substantially affect the hydrophobic character of the group.
When X is C, the detergent is called a betaine; and when X is
S:O, the detergent is called a sulfobetaine or sultaine.
Cationic surface active agents may also be employed.
They comprise surface active detergent compounds which contain an
organic hydrophobic group which forms part of a cation when the
compound is dissolved in water, and an anionic group. Typical
cationic surface active agents are amine and quaternary ammonium
compounds.
Examples of suitable synthe-tic cationic detergents
-22-
~,
2Z35~
include: normal primary amines of the formula RNH2 wherein R is
an alkyl group containing from about 12 to 15 atoms; diamines
having the formula RNHC2H4NH2 wherein R is an alkyl group contain-
ing from about 12 to 22 carbon atoms, such as N-2-aminoethyl-
stearyl amine and N-2-aminoethyl myristyl amine, amide-linked
amines such as those having the formula RlCONHC2H4NH2 wherein
Rl is an alkyl group containing about 8 to 20 carbon atoms, such
as N-2-amino ethylstearyl amide and N-amino ethylmyristyl amide;
quaternary ammonium compounds wherein typically one of the groups
linked to the nitrogen atom is an alkyl group containing about
8 to 22 carbon atoms and three of the groups linked to the nitro-
gen atom are alkyl groups which contain 1 to 3 carbon atoms,
including alkyl groups bearing inert substituents, such as phenyl
groups, and there is present an anion such as halogen, acetate,
methosulfate, etc. The alkyl group may contain intermediate
linkages such as amide which do not substantially affect the
hydrophobic character of the group, for example, stearyl amido
propyl quaternary ammonium chloride. Typical quaternary ammonium
detergents are ethyl-dimethyl-stearyl-ammonium chloride, benzyl-
dimethyl-stearyl ammonium chloride, trimethyl-stearyl ammonium
chloride, trimethyl-cetyl ammonium bromide, dimethy].-ethyl-lauryl
ammonium chloride, dimethyl-propyl-myristyl ammonium chloride,
and the corresponding methosulfates and acetates.
Ampholytic detergents are also suitable for the
invention. Ampholytic detergents are well known in the art and
many operable detergents of this class are disclosed by Schwartz,
Perry and Berch in the aforementioned "Surface Active Agents and
Detergents." Examples of suitable amphoteric detergents include:
alkyl betaiminodlpropionates, RN(C2H4COOM)2; alkyl beta-amino
propionates, RN(H)C2H4COOM; and long chain imidazole derivatives
having the general formula.
-23-
~2223S~
/CH~
N CH
Il 12
/ \ 2 2 2
OH CH2COOM
wherein in each of the above formulae R is an acyclic hydrophobic
group containing from about 8 to 18 caxbon atoms and M is a
cation to neutralize the charge of the anion. Specific operable
amphoteric detergents include the disodium salt of undecylcy
imidinium-ethoxyethionic acid-2-ethionic acid, dodecyl beta
alanine, and the inner salt of 2-trimethylamino lauric acid.
The bleachiny detergent compositions of the invention
optionally contain a detergent builder of the type commonly used
in detergent formulations. Useful builders include any of the
conventional inorganic water-soluble builder salts, such as,
for example, water-soluble salts of phosphates, pyrophosphates,
orthophosphates, polyphosphates, silicates, carbonates, and the
like. Organic buiIders include water-soluble phosphonates,
polyphosphonates, polyhydroxysulfonates, polyacetates, carboxy-
lates, polycarboxylates, succinates and the like.
Specific examples of inorganic phosphate builders
include sodium and potassium tripolyphosphates, pyrophosphates
and hexametaphosphatesO The organic polyphosphonates specifically
include, for example, the sodium and potassium salts of ethane
l-hydroxy-l,l~diphosphonic acid and the sodium and potassium
salts of ethane-1,1,2-triphosphonic acid. Examples of these and
other phosphorous builder compounds are disclosed in U.S. Patent
Nos. 3,213,030; 3,422,021; 3,422,137 and 3,400,176. Pentasodium
tripolyphosphate and tetrasodium pyrophosphate are especially
preferred water-soluble inorganic builders.
Specific examples of non-phosphorous inorqanic
builders include ~ater-soluble inorganic carbonate, bicarbonate
-24-
23~i
and silicate salts. The alkali metal, for example, sodium and
potassium, carbonates, bicarbonates and silicates are particu-
larly useful herein.
Water-soluble organic builders are also useful. For
example, the alkali metal, ammonium and substituted ammonium
acetates, carboxylates, polycarboxylates an~ polyhydroxysulfon-
ates are useful builders for the compositions and processes oE
the invention. Specific examples of acetate and polycarboxylate
builders include sodium, potassium, lithium~ ammonium and sub-
stituted ammonium salts of ethylene diaminetetracetic acid,nitrilotriacetic acid,benzene polycarboxylic (l.e. penta- and
tetra-) acids, carboxymethoxysuccinic acid and citric acid.
Water-insoluble builders may also be used, particu-
larly, the complex silicates and more particularly, the complex
sodium alumino silicates such as, zeolites, e.g., zeolite 4A,
a type of zeolite molecule wherein the univalent cation is
sodium and the pore size is about 4 Angstroms. The preparation
of such type zeolite is described in U.S. Patent 3,114,603.
The zeolites may be amorphous or crystalline and have water of
hydration as known in the art.
The use of an inert, water-soluble filler salt is
desirable in the laundering compositions of the invention. A
preferred filler salt is an alkali metal sulfate, such as,
potassium or sodium sulfate, the latter being especially
preferred~
Various adjuvants may be included in the laundry
detergent compositions of the invention~ In general, these
include perfumes; colorants, e.g., pigments and dyes; bleaches,
such as, sodium perborate, antiredeposition agents, such as,
alkali metal salts of carboxymethylcellulose; optical brighteners,
such as, anionic, cationic or nonionic brighteners; Eoam stabil-
izers, such as alkanolamides, and the like,all of which are well-
-25-
35~
known in the fabric washing art for use in detergent compositions.
Flow promoting agents, commonly referred to as flow aids, may
also be employed to maintain the particulate compositions as free-
flowing beads or powder. ~tarch derivatives and special clays
are commerically available as additives which enhance the
flowability of otherwise tacky or pasty particulate compositions,
two of such clay additives being presently marketed under the
-t.rade marks '~Satintone" and "Microsil".
The fabric softening composi-tions of the invention
are advantageously incorporated into laundry detergent compos-
itions which are specifically intended for hand-wash operations.
There are three general types of such hand-wash detergents which
are particularly useful for the present invention. The first
type typically comprises: (a) from about 5 to about 50%, by
weight, of an alkyl benzene sulfonate detergent; (b) from about
0 to about 20%, by weight, of a nonionic detergent compound;
(c) from about 0 to about 20%, by weight, of a soap; (d) from
about 5 to about 50%, by weight, of pentasodium tripolyphos-
phate; (e) from about 5 to about 25%, by weight, of sodium
silicate; (f) from about 0 to about 1%, by weight, of carboxy
methylcellulose; and, (g) the balance comprising water, sodium
sulfate and optionally minor components such as perfume and
brighteners.
The second type of hand-wash detergent composition
compriseso ~a) from about 5 to about 25%, by weight, of a non-
ionic detergent compound: (b) from about 5 to about 80%, by
weight, of a detergent builder salt; (c) from about 0 to 10%, by
weight, of sodium silicate; (d) from about 0 to 5%, by weight,
of a soap; and (e) the balance comprising water and optionally
minor components such as perfume and optical brighteners. The
third type of hand-wash composition comprises: (a) at least 90%,
by weight, of a soap; (b) from about 0 to about 1%, by weight,
-26-
of carboxymethylcellulose; and, (c) the balance comprising water
and optionally minor components such as perfume and optical
brigh~eners.
The following examples are provided to further
illustrate the invention. It is to be unclerstood, however, that
such examples are intended solely for purposes of illustration
and the invention is not to be limited thereby.
EXAMPLE 1
Agglomeratés of Thixojel No. 1(1) clay were used in
the present examples and were prepared by the procedure des-
cribed below wherein the following components were used:
Thixojel No. 1 clay (325 mesh) and an aqueous agglomerating
solution containing 7% of sodium silicate in a ratio of
Na2O:SiO2 of about 1:2.4.
The agglomerates were prepared in a rotary drum
characterized by a 19.5 inch diameter, a 23.5 inch length and
an a~is of rotation adjustable between ten and ninety degrees from
the vertical.
9.1 kg. of the Thixojel No. 1 clay was charged into
the above-described rotary drum which was aligned at an angle
of 20 degrees from the vertical. 3.2 kg. of the aqueous sili-
cate solution at a temperature of 43C was sprayed on to the
clay while the drum was rotating at about 6 rpm. The axis of the
rotary drum was then adjusted to an angle of 70 degrees from the
vertical and an additional 3.2 kg. of silicate solution was
sprayed on to the clay. The resulting wet agglomerates of clay
were trans~erred in 2 kg. portions to an Aeromatic ST-5 (trade-
1~ tradename of a Wyoming bentonite clay sold by Georgia Kaolin
Co., Elizabeth, New Jersey.
-27-
23~i~
mark) fluid bed dryer, manufactured by Aeromatic Corp.,
Summerville, New Jersey, and dried to approximately 10 wt.%
moisture using an air flow rate of about 6,000 liters per minute
and an air inlet temperature of 71C. Dry:ing was effected in
about 15 minutes. The dried material was then passed through
a Stokes granulator having a 40 mesh screen, the product particle
size being between 40-100 mesh. The fines passing through a 100
mesh screen were recycled to the rotary drum.
Surface modified clay particles in accordance with
the invention were used in the present examples and prepared as
follows.
100 g. of the bentonite agglomerates prepared as described above
were put into a one-liter laboratory-model drum which was rotated
by a motor at about 10 rpm. Two grams of Varisoft*3690(1) were
added drop-wise to the clay while the drum was rotating so as
to simulate in the laboratory-scale equipment the effect of
spraying the QA compound upon the clay. The amount of QA com-
pound relative to t~e clay (based on the active ingredient in
the Varisoft 3690) is 0.15g./lOg. clay. The resultlng particles
are referred to in the examples as "coated" particles of agglom-
erated clay.
A granular detergent formulation "A" was used in
the tests described below and had the following composition:
.... _ . _ ~
lMethyl (1) oleyl amido ethyl (2) oleyl imidazolinium-methyl sul-
fate (75% active ingredients in 25% isopropanol) manufactured by
Sherex Chemical Company, Dublin, Ohio.
-28-
'',
~23!~
COMPOSI~ION A
ComponentWeight Percent
_
Sodium tridecyl benzene sulfonate15
Nonionic surfactant (C12 - C15 ethoxylatecl 0.5
primary alcohol, 6.5 moles EO/mole alcohol)
Pentasodium tripolyphosphate (TPP) 33
Sodium silicate (lNa20:2.4Si02) 7
Sodium sulfate 35
Moisture 9
Optical brighteners (Tinopal 5BM)0.2
CarboY~ymethyl cellulose 0.25
Comparative tests were run on swatches of terry
cloths using in one test a wash solution containing only
composition A; in the second test, a wash solution was used
containing composition A plus the above-described particles of
agglomerated clay; and in the third test, the wash solution
contained detergent composition A plus coated particles of
agglomerated clay. Washing was carried out in a one-liter
solution at 70%F. The wash conditions comprised a 10-minute
soak period followed by a l-minute hand wash. The washed and
dried swatches were graded tactilely for softness and assigned
an integer grade from 1-10 on a linear scale, the higher grades
corresponding to the softer materials. The results of the
softening tests appear in Table I.
.
-29
3~
TABLE I
Experiment Composition of wash solution Softness Raking
.
1 3.5 g/l Composition A
2 3.5 g/l Composition A + 6
0.7 g/l Thixojel agglomerates
; 3 3.5 g/l Composition A + 8
0.7 g/l coated Thixojel agglomerates
As evident from the data in Table I, the use of the
fabric softening composition of the invention (Experiment 3)
provided a marked improvement in softness as compared to the
use of Thixojel agglomerates having no surface coating of QA
compound (Experiment 2).
EXAMPLE 2
Thixojel No. 1 clay was agglomerated as described in
example 1 and coated with Varisoft 475(1) following the general
procedure set forth in example 1. Comparative tests were run
in Experiments 4-7 described below on swatches of terry cloths
using the washing conditions and softness rating described in
example 1. In Experiment 4, the wash solution contained a
detergent composition, but no clay or QA compound; in Experiment
5, uncoated clay agglomerates were added to the detergent
solution; in ~xperiment 6, coated agglomerates and the QA
compound were added to the wash solution as separate components.
The results of the softening tests appear in Table II below.
.
(1) ~ethyl (1) tallow amido ethyl (2) tallow imidazolinium -
methyl sulfate (75% active ingredients in 25% propylene glycol)
manufactured by Sherex Chemical Company, Dublin, Ohio.
-30-
,~ ,J
~ABLE Il
Experiment Composition of Wash Solution Softness Rating
_ _ _ _
~ 3.5 g/l Composition A
3.5 g/1 Composition A 5
0.7 g/l Thixojel agglomerates
6 3.5 g/l Composition A
0.7 g/l coated Thixojel agglomerates
(containing 0.014 g. Varisoft ~75~
7 3.5 g/l Composition A 6
0.7 g/l Thixojel ~
0.014 g/l Varisoft 475
As seen from Table II, the wash solution containing
the softening composition of the invention (Experimen~ 6)
provided significantly improved softening relative to the use
of uncaoted clay (Experiment 5) and/or -the use of Thixojel and
QA compound as independent components of the wash solution
(Experiment 7). Thus, Experiment 7 demonstrates that the
surprisingly improved softening effects which are provided by
the softening compositions of the invention (Experiment 6)
cannot be duplicated by simply adding the individual components
of the present compositions to the wash solution.
Improved softening is also achieved in accordance
with the invention by coating the Thixogel agglomerates des-
cribed in example 1 with one of the following amines, diamines
and diamine salts: primary tallow amine, secondary tallow
methyl amine, tritallow amine, N-coco-1,3-diami.nopropane, N-
tallow-1,3-diaminopropane and N-tallow-1,3-diaminopropane
diacetate.
-31-
